Detergent composition and process of manufacturing same



Patented Oct. 15, 1940 DETERGENT COMPOSITION AND rnocass MANUF o'roam OF A GSAME Lucas P. Kyrides, Webster Groves, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing.

Application March 1, 1938, Serial No. 193,348

- 11 Claims. (01. 266-505) The present invention relates to a new and improved detergent composition and its process of manufacture.

It is known to halogenate kerosene and condense the'halide so formed with aromatic hydrocarbons and sulfonate the resulting condensate for use as a detergent. Such processes as heretofore employed used wide fractions of kerosene, and generally wide fractions of kerosene containing undesirable impurities which produced a relatively impure detergent on condensing with the aromatic compound and sulfonating. Again it has heretofore been believed that mono-halogenation of the kerosene fraction only was desired and that the mono-halide so formed only maybe advantageously employed in the production of the detergent, and in consequence it was necessary to discard any alkylation products which resulted from any higher halogenation products formed in the halogenation. To maintain this mono-halogenation, the amount of halogenation has heretofore been restricted to a low molecular ratio and preferably below one-third of that required to form the monohalide. This has necessitated handling large volumes of materials and has consequently greatly increased the cost of the final detergent product.

In accordance with. the present invention a greatly improved product has been obtained over that heretofore taught by the prior art. Furthermore, it has beendiscovered according to the ptresent improved process that not only may mono-halogenated kerosene fractions be employed in the condensation step with the aromatic compounds, but that poly-halogenated kerosene fractions may be employed as well. Such a process as now employed has resulted in an improved product and a great saving in the cost of the final detergent product. In the operation of the present invention, it has been found preferable that the kerosene fraction be substantially free from olefines, aromatic compounds, sulfur compounds and be substantially water-white in color. Furthermore, as the unreacted kerosene fractions of higher boiling ranges possess a distilling range near to that of alkylated aromatic compounds, as for example, alkyl benzene, great care must be taken in its removal from the condensation product in order to make certain it has been removed entirely, and

that in its removal, contamination or decomposition of the alkyl aromatic compound has not been effected. In operating the'process of this invention, this undesirable decomposition and contamination has been obviated.

Furthermore, it has been found that the polyhalogenated paraflins derived from the particular kerosene fraction of the present invention may be condensed with an aromatic compound, as for example an aromatic hydrocarbon, in the presence of a suitable condensation catalyst, as for example aluminum chloride, to produce compounds other than mono-alkylated products, which may be called 'poly-arylated alkanes, and the resulting poly-arylated alkanes sulfonated with a su.table sulfonating agent to produce a lighter colored product than has heretoforebeen obtained. While the entire halogenated kerosene fraction is condensed with the aromatic compound, and the resulting product sulfonated according to the preferred process, it may be desirable to distill the alkylated aromatic compounds and separate them from a dark colored high boiling tarry residue in order to obtain the highest detergency and lightest colored product.

It is surprising to learn that when the socalled-poly-arylated alkanes, derived from a condensation of a poly-halogenated kerosene fraction and an aromatic compound, are sulfonated and employed alone as detergents, they are rela. tively low in detergent efliciency, as compared to the sulfonated condensation product of the corresponding mono-halogenated kerosene fraction and the same aromatic compound, yet when the sulfonated poly-arylated alkanes employed admixed with this same sulfonated condensation product of the mono-halogenated kerosene fraction and the corresponding aromatic compound,

, the combined detergent eflect issubstantially the same as is that of the product resulting from the mono-halogenated kerosene fraction alone. This is an unforeseen result. Just what the co-action is, it is difllcult to state, but apparently different types of detergencytake place with an improved total cleaning effect. i

In the operation of this invention, it is preferred that a kerosene fraction having a distilling Five hundred ten (510) parts by weight of a kerosene distillate having a distilling range of substantially 205 C. to 245 C. and being substantially free of oleflnes, aromatic and sulfur commands, were chlorinated substantially 50% of theextent stoichiometrically required to form the monochloride at a temperature of C. The mixture of alkyl halide and unhalogenated kerosene was then added at room temperature with agitation to 350 parts by weight of benzene containing 15 parts by weight of anhydrous aluminum chloride. On completion of the addition of the alkyl halide-kerosene mixture, the reactants were heated for an additional period of two hours at 50 C. On the completion of the reaction, the reaction product consists of two layers. The upper layer comprising unchanged benzene, kerosene and alkyl benzene, is separatedfrom the lower or catalyst layer, and the benzene removed by distillation at atmospheric pressure. The unreacted kerosene fraction is removed preferably by distillation at reduced pressure in order to avoid decomposition of the alkyl benzene. The residue comprising the mixed alkyl benzenes of the present invention and mainly mono-alkylated benzene and so-called poly-phenylated alkanes, may be sulfonated without further purification or may be distilled to remove any tarry residual byproducts, which I have found adversely affect the detergent properties of the desired product. The alkyl benzenes derived from the mono-halogenated and poly-halogenated kerosene fraction, whether crude or distilled, are carefully sulfonated employing a process so as to obtain a light colored product after conversion to their water-soluble salts. Thus, one convenient method of sulfonation, which produces such a product, comprises the use of 96% sulfuric acid n the ratio of substantially 300 parts by weight of acid to substantially-100 P rts by weight of alkyl benzene at substantially 40 C. to 50 C. Another method of sulfonation, which produces a light colored product, comprises the use of 20% oleum in the ratio of substantially parts by weight of acid to substantially 100 parts by weight of alkyl benzene at a temperature of substantially 0 C. to 5 C. It is a preferred embodiment of this invention that the sulfonation step be carefully controlled by temperature regulation and concentration of acid so that a light colored product is obtained after neutralization of the sulfonic acid. The alkyl benzene sulfonlc acids may be separated by adding water to the sulfonation mass, whereupon the sulfonlc acids separate as an upper layer, which is drawn off and neutralized with caustic soda. The aqueous solution of the sodium salt of the alkylated benzene sulfonlc acids may be evaporated to dryness in which case the sodium salt of the alkylbenzene sulfonic acids contains varying amounts of sodium sulfate, or the sodium sulfate may be separated from the sodium salt of the alhl benzene sulfonic acid by suitable means.

In order to compare the detersive effectiveness I of the detergents obtained, the following wash test was employed.

White cotton fabric was thoroughly desized by washing successively in acid, alkaline and soapbaths, the fabric being rinsed after each bath. The fabric so obtained was repeatedly immersed in a soil comprising a suspension of colloidal graphite in a solution of a mineral and vegetable oil in carbon tetrachloride until a baryta whiteness of 27% to 30% was obtained. The fabric was then aged prior to use. his ased strips were cut into six-inch squares and placed in separate pint jars containing 100 c. c. of the solution under test and 10 rubber balls. In all cases the concentrationof the wash solution was 0.2% detergent by weight. The jars were closed, clamped in a launderometer and agitated at a temperature of F. At the end of definite periods of washing, the launderometer was stopped, the fabric removed and given two rinses with 100 c. c. portions of water. The washed fabric was dried and its whiteness determined by means of a Pulfrich photometer, wherein readings give the percent whiteness in comparison with th whiteness of baryta, and a consequent measure of efficiency of the detergent may be determined.

Tests were carried out simultaneously in the manner defined above on the following materials obtained from the sulfonation of the condensation product of halogenated kerosene boiling at 205 C. to 245 C., said kerosene halogenated to the extend of 50% of that required stoichiometrically to form the monohalide and benzene as defined above:, (A) the sodium salt of the product obtained from the sulfonation of the mono-alkyl benzenes separated from the total alkylation product .by fractionation at reduced pressure, and derived from the mono-halogenated kerosene fraction, (B) the sodium salt of the product obtained from the sulfonated polyphenylated alkanes, comprising the residue remaining after distilling of! the above monoalkyiated benzene, and derived from the polyhalogenated kerosene fraction and (C) the sodium salt of the product obtained from the sulfonation of the total crude condensation product of the entire halogenated kerosene fraction and benzene. It was found that while (B) was greatly inferior to (A) in detergent emciency, (C) was substantiailyidentical with (A) in detergent efficiency.

Detergents were also prepared in a manner analogous to that described above from a halo- .genated kerosene fraction, said kerosene fraction having a distilling range of 205 C. to 245 C.. and wherein the halogenation, for example chlorination, was 60% and 75% respectively of that required to form the monochloride. Detergent tests were also made on the following products obtained therefrom: (A') the sodium salt of the mono-allq'lated benzene, (B') the sodium salt of the sulfonated poly-phenylated alkanes and (C') the sodium salt of the sulfonated crude unfractionated total alkyl benzenes. It was found that while (0) the detergent obtained from the crude unfractionated total alkyl benzenes possessed desirable detergent action and was more efficient than was (B'), it was desirable to distill the crude alkyl benzene in order to eliminate a small proportion of tarry dark colored by-products, after which the sodium salt of the total alkyl benzene sulfonlc acids was found substantially equal to detergenteiliciency to the sodium salt of the .mono-alkylated benzene sulfonlc acid (A') above.

If desirable, of course, a narrower kerosene fraction may be halogenated, condensed with aromatic compounds, for example benzene. and the total alkylation product, either crude or distilled, sulfonated and employed as eificient detergents according to the present invention.

Thus a kerosene fraction distilling between 205 C. and 225 C. has been found to give most deprocess of this invention. Y

Again other aromatic compounds than benzene have been condensed with a halogenated kerosene fraction, said kerosene fraction distilling between 205 C. and 245 0., and the total condensate sulfonated in the 'manner defined above. Thus I may employ toluene, xylene.

dipbenyl, chlor diphenyls, naphthalene and the like, and such products are included within the scope oi the invention.

Furthermore, other salts of the alkylated aromatic sulfonic acids than the sodium salt may be employed. Water-soluble salts generally may be employed, although the alkali metal salts are preferred.

In the halogenation of the keroseneiraction of the presentinvention, other proportions 0! halogen may be employed than hereinbefore set forth in order to produce a mixture comprising monohalides and a substantial amount of poly-halides for use according to the present invention. It is preferred, however, that halogenation to the extent of morethan 33%% and less than 100% of that stoichometrically required to form the inonohalide be efiected, in order toobtain the most desirable detergent.

This application is acontinuation-in-part of my copending applications Serial No. 88,685, filed July 2, 1936, now patent 2,161,174; and Serial No.

88,625, filed July 2, 1936, now patent 2,161,173.

The present invention is limited solely by the claims attached hereto.

What is claimed is:

l. A 'detergent composition comprising as its essential detergent constituent a mixture of alkali metal salts of monosulfonated monoaryl alkanes and polyaryl alkanes obtained by halogenating a kerosene fraction having a distillation range within therange of approximately 205 C. to 245 C. until a substantial .proportion ofdihalogenated hydrocarbons admixed with monohalogenated hydrocarbons is produced therein, condensing" an aromatic hydrocarbon therewith to obtain an alkylated aromatic hydrocarbon mixture containing monoaryl alkanes and polyaryl alkanes, separating the unhalogenated kerosene fraction from the alkylated aromatic hydrocarbon mixture, sulfonating the alkylated aromatic hydrocarbon mixture and converting the resulting sulfonated product to alkali metal salts.

2. A detergent composition comprising as its essential detergent constituent a mixture of alkali metal salts of monosulfonated monoaryl alkanes and polyaryl alkanes, obtainable by halogenating a kerosene fraction having a distillation range within the range of approximately 205C. to 245 C. to the extent of less than 100% and more than 33%% of that required to form the monohallde, condensing an aromatic hydrocarbon therewith to obtain an alkylated aromatic hydrocarbon mixture containing monoaryl alkanes and polyaryl alkanes, separating the unhalogenatedkerose'ne fraction from the alkylated aromatic hydrocarbon mixture, sulfonating the alkylated=-aromatic hydrocarbon mixture and converting the resulting sulfonated product to alkali metal salts.

v3. A detergent composition comprising as its essential detergent constituent a mixture of alkali metal salts of monosulfonated monoaryl alkanes and polyaryl alkanes obtainable by chlorinating a kerosene fraction having a distillation range within the -range of approximately 205 C. to 245 C. until a substantial proportion of dichlorinated hydrocarbons admixed with monochlorinated hydrocarbons is produced therein, condensing an aromatic hydrocarbon therewith to obtain an alkylated aromatic hydrocarbon mixture containing monoaryl alkanes and polyaryl alkanes,

separating the unchlorinated kerosene fraction from the alkylated aromatic hydrocarbon mixture, sulfonating the alkylated aromatic hydrocarbon mixture and converting the resulting sulionated product to alkali metal salts.

4. A detergent composition comprising as its essential detergent constituent a mixture of alkali metal salts of monosulionated monoaryl-alkanes and polyaryl alkanes obtainable by chlorinating a kerosene fraction having a distillation range within the range of approximately 205 C. to 245 C. until a substantial proportion of dichlorinated hydrocarbons admixed with monochlorinated hydrocarbons is produced therein, condensing an aromatic hydrocarbon therewith to obtain an alkylated aromatic hydrocarbon mixture containing monoaryl alkanes and polyaryl alkanes, separating the unchlorinated kerosene fraction irom the alkylated armotatic hydrocarbon mixture, purifying the alkylated aromatic hydrocarbon mixture by distillation under reduced pressure, sulfonating said purified alkylated aromatic hydrocarbon mixture, and converting the resulting sulfonated product to alkali metal salts.

5. A detergent composition comprising as its essential detergent constituent a mixture of alkali metal salts of inonosulfonated monophenyl alkanes and polyphenyl alkanes obtainable by chlorinating a kerosene fraction having a distillation range within the range of approximately 205 C. to 245 C. until a substantial proportion of dichlorinated hydrocarbons admixed with monochlorinated hydrocarbons is produced therein, condensing benzene therewith to obtain' an alkylated benzene mixture containing monophenyl alkanes and polyphenyl alkanes, separating theunchlorinated kerosene fraction from the alkylated benzene mixture, sulfonating the alkylated benzene mixture and converting the resulting sulfonated product to alkali metal salts.

6. A detergent composition comprising as its essential detergent constituent a mixture-oi alkali metal salts of monosulfonated monophenyl alkanes and polyphenyl alkanes, obtainable by chlorinating a kerosene fraction having a distillation range within the range of approximately 205 C. to 245 C. to the extent of less than and more than 33 of that required to form the monochloride, condensing benzene therewith to obtain an alkylated benzene mixture containing monophenyl alkanes and polyphenyl alkanes,

separating the unchlorinated' kerosene fraction from the alkylated benzene mixture, sulfonating the alkylated benzene mixture and converting the resulting sulfonated product to alkali metal salts.

7. A detergent composition comprising as its essential .detergent constituent 'a mixture of alkali metal salts of monosulionated monophenyl alkanes and polyphenyl alkanes obtainable by chlorinating a kerosene fraction having a distillation range within the range of approximately 205 C. to 245 C. until a substantial proportion of. dichlorinated hydrocarbons admixed with monochlorinated hydrocarbons is produced therein, condensing benzene therewith to obtain an alkylated benzene mixture containing monophenyl alkanes and polyphenyl alkanes, separating the unchlorinated kerosene fraction from the alkylated-benzene mixture, purifying the alkylated benzene mixture by distillation under reduced pressure, sulionating said purified alkylated benzene mixture, and converting the resulting sulionated product to alkali metal salts.

8. A detergent composition comprising as its essential detergent constituent a mixture of sotillatlon range within the range of approlmately 205 C. to 245 C. until a substantial proportion of dichlorlnated hydrocarbons admixed with monochlorinated hydrocarbons is produced therein, condensing benzenetherewith to obtain an alkylated benzene mixture containing monophenyl alkanes and 'polyphenyl alkanes, separating the unchlorinated kerosene fraction from the allwlated benzene mixture, sulfonating the allwlated benzene mixture and converting the resulting sulfonated product to sodium salts.

9. A detergent -composition comprising as its essential detergent constituent a mixture or sodium salts of monosulionated monophenyl alkanes and polyphenyl alkanes, obtainable by chlorinating a kerosene fraction having a distillation range within the range of approximately 205 C. to 245 C. to the extent of less than 100% and more than 33$ of that required to form the monochloride, condensing benzene therewith to obtain an alkylated benzene mixture containing monophenyl alkanes and polyphenyi alkanes, separating the unchlorinated kerosene fraction from the allnylat'ed benzene mixture, sulfonating the alkvlated benzene mixture and converting the resulting sulfonated product to sodium salts.

10. A detergent composition comprising as itsessential detergent constituent a mixture of sodilum salts of monosulfonated monophenyl alkanesand polyphenyl alkanes obtainable by chlorinating a kerosene traction having a distillation range within the range of approximate- 1y 205 C. to 245 C. until a substantial proportionof dichlorinated hydrocarbons admixed with monoehlorinated hydrocarbons is produced therein, condensing benzene therewith to obtain an aikylated benzene mixture containing monophenyl alkanes and polyphenyl alkanes, separating the unchlorinated kerosene fraction from the alkylated benzene mixture, purifying the alkylated benzene mixture, by distillation under reduced pressure, sulfonating said purified alkylated benzene mixture, and converting the resulting sultonated product to sodium salts.

11. In the process of producing an alkali metal salt of an alkylated aromatic monosulfonic acid having detergentproperties, comprising the steps of halogenating a kerosene traction distilling between 205 and 245 C., condensing an aromatic hydrocarbon therewith to form an alkylated aromatic hydrocarbon mixture, separating the unreacted kerosene fraction from said alkylated aromatic hydrocarbon mixture, sulionating the alkylated aromatic hydrocarbon mixture and transforming the resulting alkylated aromatic suifonic acid to an alkali metal salt, the improvement consisting in halogenating the kerosene fraction until a substantial proportion of dihalogenated hydrocarbons admixed with monohalogenated hydrocarbons is formed therein and thereafter condensing this halogenated fraction with the aromatic hydrocarbon.

LUCAS P. KYRIDES.

line 1, for "epproimately" read --e.pproximately-- CERTIFICATE OF CORRECTION.

Patent No. 2,218,h72. October 1 191 0.

LUCAS P. KYRIDES.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 16, for "stoichome tricelly" read --sto1chi0metr1cal1y--;line 29, claim 1, for the word obtained reed --obtaine.ble-- and second column, line 11;, claim 14., for "armotatic" read -e.romatic-.-;- page 1;, first column,

line 28-29, for "sodilum" read "sodium"; and that the said Letters Patent should be read with this correction therein that the same may contour: to the record of the case in the Patent Office.

Signed and sealed this 51"d day of December, A. D 191m.

4 Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

